2-(benzotriazol-2-yl)-4-alkyl-6-(2-hydroxy-3-benzoyl-6-alkoxybenzyl)phenols and stabilized compositions

ABSTRACT

2-(Benzotriazol-2-yl)-4-alkyl-6-(2-hydroxy-3-benzoyl-6-alkoxybenzyl)phenols am prepared by reacting a Mannich base of a 2-(2-hydroxy-5-alkylphenyl)-2H-benzotriazole with a 2-hydroxy-4-alkoxybenzophenone. The hybrid products exhibit outstanding efficacy in protecting organic substrates from light-induced deterioration as well as good resistance to loss by volatilization or exudation during the processing of stabilized compositions at elevated temperatures.

The instant invention pertains to novel2-(benzotriazol-2-yl)-4-alkyl-6-(2-hydroxy-3-benzoyl-6-alkoxybenzyl)phenolsand compositions stabilized by said compounds.

BACKGROUND OF THE INVENTION

The UV absorbers of the 2H-benzotriazole and benzophenone type have longbeen known as very effective light stabilizers for a host of organicmaterials and have enjoyed considerable commercial success.

The description, preparation and uses of the 2H-benzotriazoles UVabsorbers are taught in U.S. Pat. Nos. 3,004,896; 3,055,896; 3,072,585;3,074,910; 3,189,615; 3,230,194; 4,127,586; 4,226,763; 4,278,589;4,315,848; 4,383,863; 4,675,352; 4,681,905 and 4,853,471.

The description, preparation and uses of the benzophenone UV absorbersare found in a comprehensive review by G. R. Lapin in the "Encyclopediaof Polymer Science and Technology", N. Bikales, editor, JohnWiley-Interscience, New York, Vol. 14, 197 1, pp 125-148.

In some circumstances, the benzotriazole and benzophenone UV absorbersexhibit limited compatibility with certain substrates, and/or anexcessive tendency to exude, sublime or volatilize away duringprocessing of stabilized compositions into sheets, films, fibers orother pellicles when processing must be done at elevated temperatures.Likewise, such compounds may also suffer undue loss by volatilization orsublimation from fabricated structures, particularly thin rims, coatingsor fibers, especially when such structures are subjected to elevatedtemperatures during use.

Attempts have been made to increase compatibility and to reducevolatilization by modifying the structure of the benzotriazole. U.S.Pat. No. 3,230,194 teaches that substitution of a higher alkyl group(tert-octyl) for a lower alkyl group (methyl) improves compatibility andperformance of the substituted benzotriazole in polyethylene.

Likewise in U.S. Pat. Nos. 4,278,590; 4,283,327 and 4,383,863,2-(2-hydroxy-3,5-di-tert-octylphenyl)-2H -benzotriazole is shown toexhibit an excellent combination of compatibility with and/or solubilityin numerous polymer substrates along with superior resistance to lossfrom stabilization during high temperature processing, in end-useapplications where coating or films of the stabilized compositions areexposed to ambient weathering and light, and in photographicapplications.

U.S. Pat. No. 4,675,352 teaches that liquid benzotriazoles of lowvolatility are prepared by the alkylation of preformed2-(2-hydroxy-5-methylphenyl)-2H-benzotriazole.

U.S. Pat. Nos. 3,936,305; 4,681,905; 4,684,680; 4,684,679 and 5,108,835teach the2,2'-methylene-bis-[4-hydrocarbyl-6-(benzotriazol-2-yl)phenols]havinghigh molar activities and low volatility.

U.S. Pat. Nos. 3,399,237 and 4,169,089 and Japanese patent applicationsSho 53-113849; 57-6470; 49-78692; 50-74579 and 50-86487 teach thecorresponding class of low volatility compounds with high molaractivities which are the methylene-bis(2-hydroxybenzophenones).

U.S. Pat. No. 5,166,355 describes a process for making2,2'-methylene-bis-[6-(2H-benzotriazo-2-yl)-4 -hydrocarbylphenol] or5,5'-methylene-bis-(2-hydroxy-4-alkoxybenzophenone usingbis(dialkylamino)methane.

The instant compounds exhibit low volatility and excellent absorptioncharacteristics in a broad ultraviolet range. Their photographicinertness is particularly useful in photographic compositions,especially in protecting color dye images against the harmful effects ofultraviolet light.

OBJECTS OF THE INVENTION

One object of this invention is to provide some novel UV absorbershaving superior stabilization efficacy.

Another object of the invention is to provide novel photographicelements protected from the adverse effects of actinic light by theincorporation therein of the instant compounds of this invention.

DETAILED DISCLOSURE

This invention pertains to2-(benzotriazol-2-yl)-4-alkyl-6-(2-hydroxy-3-benzoyl-6-alkoxybenzyl)phenols and compositions stabilized by said compounds. Such compositionsinclude photographic elements, polymer substrates, coatings, fibers andfilms. More particularly, the instant invention relates to compounds offormula I ##STR1## wherein T₁ is hydrogen, chloro, alkyl of 1 to 4carbon atoms or --SO₃ H,

T₂ is alkyl of 1 to 12 carbon atoms,

E₁ is hydrogen, chloro or --OE₂,

E₂ is hydrogen or alkyl of 1 to 18 carbon atoms,

E₃ is hydrogen, alkyl of 1 to 4 carbon atoms, chloro or --SO₃ H,

E₄ is hydrogen, chloro or --OE₅,

E₅ is hydrogen or alkyl of 1 to 18 carbon atoms, and

E₆ is hydrogen, hydroxyl or carboxy.

Preferably, T₁ is hydrogen or chloro; most preferably, hydrogen.

Preferably T₂ is alkyl of 1 to 12 carbon atoms; most preferably alkyl of1 to 8 carbon atoms.

Preferably E₁ is --OE₂ where E₂ is hydrogen or alkyl of 1 to 12 carbonatoms; most preferably where E₂ is hydrogen or alkyl of 1 to 8 carbonatoms.

Preferably E₃ is hydrogen.

Preferably E₄ is hydrogen or --OE₅ where E₅ is hydrogen or alkyl of 1 to12 carbon atoms; most preferably where E₅ is hydrogen or alkyl of 1 to 4carbon atoms.

Preferably E₆ is hydrogen or hydroxyl.

Especially preferred are the compounds where T₁ is hydrogen or chloro,T₂ is alkyl of 1 to 12 carbon atoms, E₁ is --OE₂ where E₂ is hydrogen ofalkyl of 1 to 12 carbon atoms, E₃ is hydrogen, E₄ is hydrogen or --OE₅where E₅ is hydrogen or alkyl of 1 to 12 carbon atoms, and E₆ ishydrogen or hydroxyl.

Still more preferred are the compounds where T₁ is hydrogen, T₂ is alkylof 1 to 8 carbon atoms, E₁ is --OE₂ where E₂ is alkyl of 1 to 12 carbonatoms, and each of E₃, E₄ and E₆ is hydrogen.

When any of T₁ to E₆ is alkyl, such groups are, for example, methyl,ethyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, tert-amyl,2-ethylhexyl, isooctyl, tert-octyl, lauryl, tert-dodecyl, tridecyl,n-hexadecyl and n-octadecyl.

The instant invention also pertains to stabilized compositions whichcomprise

(a) an organic material subject to degradation by the imposition ofactinic light, and

(b) an effective stabilizing amount of a compound of formula I asdescribed supra.

The instant compounds are prepared making a Mannich base of a2H-benzotriazole having the 3-position on the phenyl ring unoccupied andreacting said Mannich base with a benzophenone. The benzophenones andsaid 2H-benzotriazoles are largely items of commerce or can be easilyprepared by methods known to those of ordinary skill in the art. Theinstant compounds can also be made by making a Mannich base of thebenzophenone and reacting it with an appropriate 2H-benzotriazole.

The instant compounds exhibit good resistance to volatilization, haveenhanced solubility in selected solvents, have desirable ultravioletabsorption characteristics and are photographically inert. Thiscombination of properties makes them particularly useful in photographiccompositions especially in protecting color dye images against theharmful effects of ultraviolet light.

The instant compounds are useful as ultraviolet absorbers inphotographic gelatin layers. The compounds show maximum absorption inthe near ultraviolet and sharp cut-off just outside the visible region.The compounds are essentially colorless, are readily dispersed ordissolved by either solvent-dispersion or imbibition methods and arephotographically inert.

The instant compounds exhibit excellent compatibility characteristics inthe gelatin layers of the photographic composition which lead tocompositions essentially without haze coupled with superior protectionof the color dye images against the harmful effects of ultravioletradiation. This combination of properties clearly distinguishes theinstant compounds over the closest compounds of the prior art.

Preferably the organic material is a synthetic polymer. Such polymersare especially those containing aromatic moieties such as polystyrene,graft copolymers of styrene such as ABS resins, polyphenylene oxides,polyphenylene sulfides, polyurethanes, polyureas, polyimides,polyamide-imides, aromatic polyesters, polycarbonates, polysulfones,polyethersulfones, polyetherketones, alkyl resins, aminoplast resins andepoxy resins.

Another class of synthetic polymers of especial importance are thepolyolefins, such as polypropylene.

In general polymers which can be stabilized include

1. Polymers of monoolefins and diolefins, for example polyethylene(which optionally can be crosslinked), polypropylene, polyisobutylene,polybutene-1, polymethylpentene-1, polyisoprene or polybutadiene, aswell as polymers of cycloolefins, for instance of cyclopentene ornorbornene.

2. Mixtures of the polymers mentioned under 1 ), for example mixtures ofpolypropylene with polyisobutylene.

3. Copolymers of monoolefins and diolefins with each other or with othervinyl monomers, such as, for example, ethylene/propylene,propylene/butene-1, propylene/isobutylene, ethylene/butene-1,propylene/butadiene, isobutylene/isoprene, ethylene/alkyl acrylates,ethylene/alkyl methacrylates, ethylene/vinyl acetate or ethylene/acrylicacid copolymers and their salts (ionomers) and terpolymers of ethylenewith propylene and a diene, such as hexadiene, dicyclopentadiene orethylidene- norbornene.

4. Polystyrene, poly-(α-methylstyrene).

5. Copolymers of styrene or methylstyrene with dienes or acrylicderivatives, such as, for example, styrene/butadiene,styrene/acrylonitrile, styrene/ethyl methacrylate,styrene/butadiene/ethyl acrylate, styrene/acrylonitrile/methyl acrylate;mixtures of high impact strength from styrene copolymers and anotherpolymer, such as, for example, from a polyacrylate, a diene polymer oran ethylene/propylene/diene terpolymer; and block polymers of styrene,such as, for example, styrene/butadiene/styrene,styrene/isoprene/styrene, styrene/ethylene/butylene/styrene orstyrene/ethylene/propylene/styrene.

6. Graft copolymers of styrene, such as, for example, styrene onpolybutadiene, styrene and acrylonitrile on polybutadiene, styrene andalkyl acrylates or methacrylates on polybutadiene, styrene andacrylonitrile on ethylene/propylene/diene terpolymers, styrene andacrylonitrile on polyacrylates or polymethacrylates, styrene andacrylonitrile on acrylate/butadiene copolymers, as well as mixturesthereof with the copolymers listed under 5), for instance the copolymermixtures known as ABS-, MBS-, ASA- or AES-polymers.

7. Halogen-containing polymers, such as polychloroprene, chlorinatedrubbers, chlorinated or sulfochlorinated polyethylene, epichlorohydrinhomo- and copolymers, polymers from halogen-containing vinyl compounds,as for example, polyvinylchloride, polyvinylidene chloride, polyvinylfluoride, polyvinylidene fluoride, as well as copolymers thereof, as forexample, vinyl chloride/vinylidene chloride, vinyl chloride/vinylacetate, vinylidene chloride/vinyl acetate copolymers, or vinylfluoride/vinyl ether copolymers.

8. Polymers which are derived from α, β-unsaturated acids andderivatives thereof, such as polyacrylates and polymethacrylates,polyacrylamide and polyacrylonitrile.

9. Copolymers from the monomers mentioned under 8) with each other orwith other unsaturated monomers, such as, for instance,acrylonitrile/butadiene, acrylonitrile/alkyl acrylate,acrylonitrile/alkoxyalkyl acrylate or acrylonitrile/vinyl halogenidecopolymers or acrylonitrile/alkyl methacrylate/butadiene terpolymers.

10. Polymers which are derived from unsaturated alcohols and amines, oracyl derivatives thereof or acetals thereof, such as polyvinyl alcohol,polyvinyl acetate, polyvinyl stearate, polyvinyl benzoate, polyvinylmaleate, polyvinylbutyral, polyallyl phthalate or polyallyl-melamine.

11. Homopolymers and copolymers of cyclic ethers, such as polyalkyleneglycols, polyethylene oxide, polypropylene oxide or copolymers thereofwith bis-glycidyl ethers.

12. Polyacetals, such as polyoxymethylene and those polyoxymethyleneswhich contain ethylene oxide as comonomer.

13. Polyphenylene oxides and sulfides, and mixtures of polyphenyleneoxides with polystyrene.

14. Polyurethanes which are derived from polyethers, polyesters orpolybutadienes with terminal

hydroxyl groups on the one side and aliphatic or aromaticpolyisocyanates on the other side, as well as precursors thereof(polyisocyanates, polyols or prepolymers).

15. Polyamides and copolyamides which are derived from diamines anddicarboxylic acids and/or from aminocarboxylic acids or thecorresponding lactams, such as polyamide 4, polyamide 6, polyamide 6/6,polyamide 6/10, polyamide 11, polyamide 12,poly-2,4,4-trimethylhexamethylene terephthalamide, poly-p-phenyleneterephthalamide or poly-m-phenylene isophthalamide, as well ascopolymers thereof with polyethers, such as for instance withpolyethylene glycol, polypropylene glycol or polytetramethylene glycols.

16. Polyureas, polyimides and polyamide-imides.

17. Polyesters which are derived from dicarboxylic acids and diolsand/or from hydroxycarboxylic acids or the corresponding lactones, suchas polyethylene terephthalate, polybutylene terephthalate,poly-1,4-dimethylol-cyclohexane terephthalate,poly-[2,2-(4-hydroxyphenyl)-propane] terephthalate andpolyhydroxybenzoates as well as block-copolyether-esters derived frompolyethers having hydroxyl end groups.

18. Polycarbonates.

19. Polysulfones, polyethersulfones and polyetherketones.

20. Crosslinked polymers which are derived from aldehydes on the onehand and phenols, ureas and melamines on the other hand, such asphenol/formaldehyde resins, urea/formaldehyde resins andmelamine/formaldehyde resins.

21. Drying and non-drying alkyl resins.

22. Unsaturated polyester resins which are derived from copolyesters ofsaturated and unsaturated dicarboxylic acids with polyhydric alcoholsand vinyl compounds as crosslinking agents, and also halogen-containingmodifications thereof of low flammability.

23. Thermosetting acrylic resins, derived from substituted acrylicesters, such as epoxy-acrylates, urethane-acrylates or polyesteracrylates.

24. Alkyl resins, polyester resins or acrylate resins in admixture withmelamine resins, urea resins, polyisocyanates or epoxide resins ascrosslinking agents.

25. Crosslinked epoxide resins which are derived from polyepoxides, forexample from bis-glycidyl ethers or from cycloaliphatic diepoxides.

26. Natural polymers, such as cellulose, rubber, gelatin and derivativesthereof which are chemically modified in a polymer homologous manner,such as cellulose acetates, cellulose propionates and cellulosebutyrates, or the cellulose ethers, such as methyl cellulose.

27. Mixtures of polymers as mentioned above, for example PP/EPDM,Polyamide 6/EPDM or ABS, PVC/EVA, PVC/ABS, PVC/HVIBS, PC/ABS, PBTP/ABS.

28. Naturally occurring and synthetic organic materials which are puremonomeric compounds or mixtures of such compounds, for example mineraloils, animal and vegetable fats, oil and waxes, or oils, fats and waxesbased on synthetic esters (e.g. phthalates, adipates, phosphates ortrimellitates) and also mixtures of synthetic esters with mineral oilsin any weight ratios, which materials may be used as plasticizers forpolymers or as textile spinning oils, as well as aqueous emulsions ofsuch materials.

29. Aqueous emulsions of natural or synthetic rubber, e.g. natural latexor latices of carboxylated styrene/butadiene copolymers.

30. Polysiloxanes such as the soft, hydrophilic polysiloxanes described,for example, in U.S. Pat. No. 4,259,467; and the hardpolyorganosiloxanes described, for example, in U.S. Patent No.4,355,147.

31. Polyketimines in combination with unsaturated acrylicpolyacetoacetate resins or with unsaturated acrylic resins. Theunsaturated acrylic resins include the urethane acrylates, polyetheracrylates, vinyl or acryl copolymers with pendant unsaturated groups andthe acrylated melamines. The polyketimines are prepared from polyaminesand ketones in the presence of an acid catalyst.

32. Radiation curable compositions containing ethylenically unsaturatedmonomers or oligomers and a polyunsaturated aliphatic oligomer.

33. Epoxymelamine resins such as light-stable epoxy resins crosslinkedby an epoxy functional coetherified high solids melamine resin such asLSE-4103 (Monsanto).

In general, the compounds of the present invention are employed in fromabout 0.01 to about 5% by weight of the stabilized composition, althoughthis will vary with the particular substrate and application. Anadvantageous range is from about 0.5 to about 2%, and especially 0.1 toabout 1%.

The stabilizers of the instant invention may readily be incorporatedinto the organic polymers by conventional techniques, at any convenientstage prior to the manufacture of shaped articles therefrom. Forexample, the stabilizer may be mixed with the polymer in dry powderform, or a suspension or emulsion of the stabilizer may be mixed with asolution, suspension, or emulsion of the polymer. The resultingstabilized polymer compositions of the invention may optionally alsocontain from about 0.01 to about 5%, preferably from about 0.025 toabout 2%, and especially from about 0.1 to about 1% by weight of variousconventional additives, such as the materials listed below, or mixturesthereof.

1. Antioxidants

1.1. Alkylated monophenols, for example:

2,6-di-tert-butyl-4-methylphenol

2-tert-butyl-4,6-dimethylphenol

2,6-di-tert-butyl-4-ethylphenol

2,6-di-tert-butyl-4-n-butylphenol

2,6-di-tert-butyl-4-i-butylphenol

2,6-di -cyclopentyl-4-methylphenol

(α-methylcyclohexyl)-4,6-dimethylphenol

2,6-di-octadecyl-4-methylphenol

2,4,6-tri-cyclohexylphenol

2,6-di-tert-butyl-4-methoxymethylphenol

1.2. Alkylated hydroquinones, for example:

2,6-di-tert-butyl-4-methoxyphenol

2,5-di-tert-butyl-hydroquinone

2,5 -di-tert-amyl-hydroquinone

2,6-diphenyl-4-octadecyloxyphenol

1.3. Hydroxylated thiodiphenyl, ethers, for example:

2,2'-thio-bis-(6-tert-butyl-4-methylphenol)

2,2'-thio-bis-(4-octylphenol)

4,4'-thio-bis-(6-tert-butyl-3-methylphenol)

4,4'-thio-bis-(6-tert-butyl-2-methylphenol)

1.4. Alkylidene-bisphenols, for example:

2,2'-methylene-bis-(6-tert-butyl-4-methylphenol)

2,2'-methylene-bis-(6-tert-butyl-4-ethylphenol)

2,2'-methylene-bis-[4-methyl-6-(α-methylcyclohexyl)-phenol]

2,2'-methylene-bis-(4-methyl-6-cyclohexylphenol)

2,2'-methylene-bis-(6-nonyl-4-methylphenol)

2,2'-methylene-bis-[6-(α-methylbenzyl)-4-nonylphenol]

2,2'-methylene-bis-[6-(α,α-dimethylbenzyl)-4-nonylphenol]

2,2'-methylene-bis-(4,6-di-tert-butylphenol)

2,2'-ethylidene-bis-(4,6-di-tert-butylphenol)

2,2'-ethylidene-bis-(6-tert-butyl-4-isobutylphenol)

4,4'-methylene-bis-(2,6-di-tert-butylphenol)

4,4'-methylene-bis-(6-tert-butyl-2-methylphenol)

1,1-bis-(5-tert-butyl-4-hydroxy-2-methylphenyl-butane

2,6-di-(3-tert-butyl-5-methyl-2-hydroxybenzyl)-4-methylphenol

1,1,3-tris-(5-tert-butyl-4-hydroxy-2-methylphenyl)-butane

1,1-bis-(5-tert-butyl-4-hydroxy-2-methylphenyl)-3-n-dodecylmercaptobutaneethyleneglycol bis-[3,3-bis-(3'-tert-butyl-4'-hydroxyphenyl)-butyrate]

di-(3-tert-butyl-4-hydroxy-5-methylphenyl)-dicyclopentadiene

di-[2-(3'-tert-butyl-2'-hydroxy-5'-methyl-benzyl)-6-tert-butyl-4-methylphenyl]terephthalate.

1.5. Benzyl compounds, for example:

1,3,5-tri-(3,5-di-ten-butyl-4-hydroxybenzyl)-2,4,6-trimethylbenzene

di-(3,5-di-tert-butyl-4-hydroxybenzyl)sulfide

3,5-di-tert-butyl-4-hydroxybenzyl-mercapto-acetic acid isooctyl ester

bis-(4-ten-butyl-3-hydroxy-2,6-dimethylbenzyl)dithiol terephthalate

1,3,5-tris-(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate

1,3,5-tris-(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)isocyanurate

3,5-di-tert-butyl-4-hydroxybenzyl-phosphoric acid dioctadecyl ester

3,5-di-tert-butyl-4-hydroxybenzyl-phosphoric acid monoethyl ester,calcium-salt

1.6. Acylaminophenols, for example:

4-hydroxy-lauric acid anilide

4-hydroxy-stearic acid anilide

2,4-bis-octylmercapto-6-(3,5-tert-butyl-4-hydroxyanilino)-s-triazineoctyl-N-(3,5-di-tert-butyl-4-hydroxyphenyl)-carbamate

1.7. Esters of β-(3,5-di-tert-butyl-4-hydroxyphenyl)-propionic acid withmonohydric or polyhydric alcohols, for example:

    ______________________________________                                        methanol       diethylene glycol                                              octadecanol    triethylene glycol                                             1,6-hexanediol pentaerythritol                                                neopentyl glycol                                                                             tris-hydroxyethyl isocyanurate                                 thiodiethylene glycol                                                                        di-hydroxyethyl oxalic acid diamide                            ______________________________________                                    

1.8. Esters of β-(5-tert-butyl-4-hydroxy-3-methylphenyl)-propionic acidwith monohydric or polyhydric alcohols, for example:

    ______________________________________                                        methanol       diethylene glycol                                              octadecanol    triethylene glycol                                             1,6-hexanediol pentaerythritol                                                neopentyl glycol                                                                             tris-hydroxyethyl isocyanurate                                 thiodiethylene glycol                                                                        di-hydroxyethyl oxalic acid diamide                            ______________________________________                                    

1.9. Amides of β-(3,5-di-tert-butyl-4-hydroxyphenyl)-propionic acid, forexample:

N,N'-di-(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)-hexamethylenediamine

N,N'-di-(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)-trimethylenediamine

N,N'-di-(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)-hydrazine

1.10 Diarylamines, for example:

diphenylamine, N-phenyl- 1-naphthylamine, N-(4-tert-octylphenyl)-1-naphthylamine,

4,4'-di-tert-octyl-diphenylamine, reaction product ofN-phenylbenzylamine and

2,4,4-trimethylpentene, reaction product of diphenylamine and2,4,4-trimethylpentene, reaction product of N-phenyl-1-naphthylamine and2,4,4-trimethylpentene.

2. UV absorbers and light stabilizers

2.1.2-(2.'-Hydroxyphenyl)-benzotriazoles, for example, the 5'-methyl-,3',5'-di-ten-butyl-, 5-tert-butyl-, 5'-(1,1,3,3-tetramethylbutyl)-,5-chloro-3',5'-di-tert-butyl-, 5-chloro -3'-tert-butyl-5'-methyl-,3'-sec-butyl-5'-tert-butyl-, 4-octoxy, 3',5'-di-tert-amyl-,3',5'-bis-(α,α-dimethylbenzyl),3'-tert-butyl-5'-(2-(omega-hydroxy-octa-(ethyleneoxy)carbonyl-ethyl)-,3'-dodecyl-5'-methyl-, and 3'-tert-butyl-5'-(2-octyloxycarbonyl)ethyl-,and dodecylated-5'-methyl derivatives.

2.2. 2-Hydroxy-benzophenones, for example, the 4-hydroxy-, 4-methoxy-,4-octoxy, 4-decyloxy-, 4-dodecyloxy-, 4-benzyloxy, 4,2',4'-trihydroxy-and 2'-hydroxy-4,4'-dimethoxy derivatives.

2.3. Esters of optionally substituted benzoic acids, for example, phenylsalicylate, 4-tert-butylphenyl salicylate, octylphenyl salicylate,dibenzoylresorcinol, bis-(4-tert-butylbenzoyl)-resorcinol,benzoylresorcinol, 3,5-di-tert-butyl-4-hydroxybenzoic acid2,4-di-tert-butylphenyl ester and 3,5-di-tert-butyl-4-hydroxybenzoicacid hexadecyl ester.

2.4. Acrylates, for example, α-cyano-β,β-diphenylacrylic acid ethylester or isooctyl ester or isooctyl ester, α-carbomethoxy-cinnamic acidmethyl ester, α-cyano-β-methyl-p-methoxy-cinnamic acid methyl ester orbutyl ester, α-carbomethoxy-p-methoxy-cinnamic acid methyl ester,N-(β-carbomethoxy-β-cyanovinyl)-2-methyl-indoline.

2.5. Nickel compounds, for example, nickel complexes of2,2'-thio-bis-[4-(1,1,3,3-tetramethylbutyl)-phenol], such as the 1:1 or1:2 complex, optionally with additional ligands such as n-butylamine,triethanolamine or N-cyclohexyl-diethanolamine, nickeldibutyldithiocarbamate, nickel salts of4-hydroxy-3,5-di-tert-butylbenzylphosphonic acid monoalkyl esters, suchas of the methyl, ethyl or butyl ester, nickel complexes of ketoximessuch as of 2-hydroxy-4-methyl-phenyl undecyl ketoxime, nickel complexesof 1-phenyl-4-lauroyl-5-hydroxy-pyrazole, optionally with additionalligands.

2.6. Sterically hindered amines, for examplebis-(2,2,6,6-tetramethylpiperidyl) sebacate,bis-(1,2,2,6,6-pentamethylpiperidyl) sebacate,n-butyl-3,5-di-tert.butyl-4-hydroxybenzyl malonic acidbis-(1,2,2,6,6-pentanemethylpiperidyl)ester, condensation product of1-hydroxyethyl-2,2,6,6-tetramethyl-4-hydroxypiperidine and succinicacid, condensation product ofN,N'-(2,2,6,6-tetramethylpiperidyl)-hexamethylenediamine and4-tert-octylamino-2,6-dichloro-s-triazine,tris-(2,2,6,6-tetramethylpiperidyl)-nitrilotriacetate,tetrakis-(2,2,6,6-tetramethyl-4-piperidyl)1,2,3,4-butanetetracarboxylate,1,1'(1,2-ethanediyl)-bis-(3,3,5,5-tetramethylpiperazinone),di-(1-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl) sebacate,di-(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl) succinate,1-octyloxy-2,2,6,6-tetramethyl-4-hydroxy-piperidine,poly-{[6-tert-octylamino-s-triazin-2,4-diyl][2-(1-cyclohexyloxy-2,2,6,6-tetramethylpiperdin-4-yl)imino-hexamethylene-[4-(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl)imino],2,4,6-tris[N-(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl)-n-butylamino]-s-triazine

2.7. Oxalic acid diamides, for example, 4,4'-di-octyloxy-oxanilide,2,2'-di-octyloxy-5,5'-di-tert-butyl-ox2,2'-di-dodecyloxy-5,5'-di-tert-butyl-oxanilide,2-ethoxy-2'-ethyl-oxanilide, N,N'-bis (3-dimethylaminopropyl)-oxalamide,2-ethoxy-5-tert-butyl-2'-ethyloxanilide and its mixture with2-ethoxy-2'-ethyl-5,4'-di-tert-butyloxanilide and mixtures of ortho- andpara-methoxy- as well as of o- and p-ethoxy-disubstituted oxanilides.

2.8. Hydroxyphenyl-s-triazines, for example2,6-bis-(2,4-dimethylphenyl)-4-(2-hydroxy-4-octyloxyphenyl)2,6-bis-(2,4-dimethylphenyl)-4-(2,4-dihydroxyphenyl)-s-triazine;2,4-bis(2,4-dihydroxyphenyl)-6-(4-chlorophenyl)-s-triazine;2,4-bis[2-hydroxy-4-(2-hydroxyethoxy)phenyl]-6-(4-chlorophenyl)-s-triazine;2,4-bis[2-hydroxy-4-(2-hydroxy-4-(2-hydroxyethoxy)phenyl]-6-(4-bromophenyl)-s-triazine;2,4-bis[2-hydroxy-4-(2-hydroxyethoxy)phenyl]-6-(4-bromophenyl)-s-triazine;2,4-bis[2-hydroxy-4-(2-acetoxyethoxy)phenyl]6-(4-chlorophenyl)-s-triazine,2,4-bis(2,4-dihydroxyphenyl)-6-(2,4-dimethylphenyl)-s-triazine.

3. Metal deactivators, for example, N,N'-diphenyloxalic acid diamide,N-salicylal-N'-salicyloylhydrazine, N,N'-bis-salicyloylhydrazine,N,N'-bis-(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hydrazine,3-salicyloylamino- 1,2,4-triazole, bis-benzylidene-oxalic aciddihydrazide.

4. Phosphites and phosphonites, for example, triphenyl phosphite,diphenylalkyl phosphites, phenyldialkyl phosphites, tri-(nonylphenyl)phosphite, trilauryl phosphite, trioctadecyl phosphite,di-stearyl-pentaerythritol diphosphite, tris-(2,4-di-tert-butylphenyl)phosphite, di-isodecylpentaerythritol diphosphite,di-(2,4-di-tert-butylphenyl)pentaerythritol diphosphite,tristearylsorbitol triphosphite, tetrakis-(2,4-di-tert-butylphenyl)4,4'-diphenylylenediphosphonite.

5. Compounds which destroy peroxide, for example, esters ofβ-thiodipropionic acid, for example the lauryl, stearyl, myristyl ortridecyl esters, mercapto-benzimidazole or the zinc salt of2-mercaptobenzimidazole, zinc dibutyl-dithiocarbamate, dioctadecyldisulfide, pentaerythritol tetrakis-(β-dodecylmercapto)-propionate.

6. Hydroxylamines, for example, N,N-dibenzylhydroxylamine,N,N-diethylhydroxylamine, N,N-dioctylhydroxylamine,N,N-dilaurylhydroxylamine, N,N-ditetradecylhydroxylamine,N,N-dihexadecylhydroxylamine, N,N-dioctadecylhydroxylamine,N-hexadecyl-N-octadecylhydroxylamine,N-heptadecyl-N-octadecylhydroxylamine, N,N-dialkylhydroxylamine derivedfrom hydrogenated tallow amine.

7. Nitrones, for example, N-benzyl-alpha-phenyl nitrone,N-ethyl-alpha-methyl nitrone, N-octyl-alpha-heptyl nitrone,N-lauryl-alpha-undecyl nitrone, N-tetradecyl-alpha-tridecyl nitrone,N-hexadecyl-alpha-pentadecyl nitrone,N-octadecyl-alpha-heptadecylnitrone, N-hexadecyl-alphaheptadecylnitrone, N-octadecyl-alpha-pentadecyl nitrone,N-heptadecyl-alpha-heptadecyl nitrone, N-octadecyl-alpha-hexadecylnitrone, nitrone derived from N,N-dialkylhydroxylamine derived fromhydrogenated tallow amine.

8. Polyamide stabilizers, for example copper salts in combination withiodides and/or phosphorus compounds and salts of divalent manganese.

9. Basic co-stabilizers, for example, melamine, polyvinylpyrrolidone,dicyandiamide, triallyl cyanurate, urea derivatives, hydrazinederivatives, amines, polyamides, polyurethanes, alkali metal salts andalkaline earth metal salts of higher fatty acids for example Castearate, Zn stearate, Mg stearate, Na ricinoleate and K palmitate,antimony pyrocatecholate or zinc pyrocatecholate.

10. Nucleating agents, for example, 4-tert-butyl-benzoic acid, adipicacid, diphenylacetic acid.

11. Fillers and reinforcing agents for example, calcium carbonate,silicates, glass fibers, asbestos, talc, kaolin, mica, barium sulfate,metal oxides and hydroxides, carbon black, graphite.

12. Other additives, for example, plasticizers, lubricants, emulsifiers,pigments, optical brighteners, flameproofing agents, anti-static agents,blowing agents and thiosynergists such as dilauryl thiodipropionate ordistearyl thiodipropionate.

The phenolic antioxidant of particular interest is selected from thegroup consisting of n-octadecyl3,5-di-tert-butyl-4-hydroxyhydrocinnamate, neopentanetetrayltetrakis(3,5-di-tert-butyl-4-hydroxyhydrocinammate), di-n-octadecyl3,5-di-ten-butyl-4-hydroxybenzylphosphonate,1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate,thiodiethylene bis(3,5-di-tert-butyl-4-hydroxyhydrocinnamate),1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene,3,6-dioxaoctamethylenebis(3-methyl-5-tert-butyl-4-hydroxyhydrocinnamate),2,6-di-tert-butyl-p-cresol, 2,2'-ethylidene-bis(4,6-di-ten-butylphenol),1,3,5-tris(2,6-dimethyl-4-tert-butyl-3-hydroxybenzyl) isocynurate,1,1,3,-tris(2-methyl-4-hydroxy-5-tert-butylphenyl)butane,1,3,5-tris[2-(3,5-di-tert-butyl-4-hydroxyhydrocinnamoyloxy)ethyl]isocyanurate,3,5-di-(3,5-di-tert -butyl-4-hydroxybenzyl)mesitol, hexamethylenebis(3,5-di-tert-butyl-4-hydroxyhydrocinnamate),1-(3,5-di-tert-butyl-4-hydroxyanilino)-3,5-di(octylthio)-s-triazine,N,N'-hexamethylene-bis(3,5-di-tert-butyl -4-hydroxyhydrocinnamamide),calcium his(ethyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate),ethylene bis[3,3-di(3-tert-butyl-4-hydroxyphenyl)butyrate], octyl3,5-di-ten-butyl-4-hydroxybenzylmercaptoacetate,bis(3,5-di-tert-butyl-4-hydroxyhydrocinnamoyl)hydrazide, andN,N'-bis[2-(3,5-di-tert-butyl-4-hydroxyhydrocinnamoyloxy)-ethyl]-oxamide.

A most preferred phenolic antioxidant is neopentanetetrayltetrakis(3,5-di-ten-butyl-4-hydroxyhydrocinnamate), n-octadecyl3,5-di-tert-butyl-4-hydroxyhydrocinnamate,1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene,1,3,5-tris(3,5-di-ten-butyl-4-hydroxybenzyl)isocyanurate,2,6-di-tert-butyl-p-cresol or2,2'-ethylidene-bis(4,6-di-tertbutylphenol).

The hindered amine compound of particular interest is selected from thegroup consisting of bis(2,2,6,6-tetramethylpiperidin-4-yl) sebacate,bis(1,2,2,6,6-pentamethylpiperidin-4-yl) sebacate,di(1,2,2,6,6-pentamethylpiperidin-4-yl)(3,5-di-tert-butyl-4-hydroxybenzyl)butylmalonate,4-benzoyl-2,2,6,6-tetramethylpiperidine,4-stearyloxy-2,2,6,6-tetramethylpiperidine,3-n-octyl-7,7,9,9-tetramethyl- 1,3,8-triaza-spiro[4.5]decane-2,4-dione,tris(2,2,6,6-tetramethylpiperidin-4-yl) nitrilotriacetate,1,2-bis(2,2,6,6-tetramethyl-3-oxopiperazin-4-yl)ethane,2,2,4,4-tetramethyl-7-oxa-3,20-diaza-21-oxodispiro[5.1.11.2]heneicosane,polycondensation product of 2,4-dichloro-6-tert-octylamino-s-triazineand 4,4'-hexamethylenebis(amino-2,2,6,6-tetramethylpiperidine),polycondensation product of1-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-hydroxypiperidine and succinicacid, polycondensation product of4,4'-hexamethylenebis-(amino-2,2,6,6-tetramethylpiperidine) and1,2-dibromoethane, tetrakis(2,2,6,6-tetramethylpiperidin-4-yl)1,2,3,4-butanetetracarboxylate,tetrakis(1,2,2,6,6-pentamethylpiperidin-4-yl)1,2,3,4-butanetetracarboxylate, polycondensation product of2,4-dichloro-6-morpholino-s-triazine and4,4'-hexamethylenebis(amino-2,2,6,6-tetramethylpiperidine),N,N',N",N"'-tetrakis[(4,6-bis(butyl-2,2,6,6-tetramethyl-piperidin-4-yl)-amino-s-triazin-2-yl]-1,10-diamino-4,7-diazadecane,mixed[2,2,6,6-tetramethylpiperidin-4-yl/β,β,β',β'-tetramethyl-3,9-(2,4,8,10-tetraoxaspiro[5.5]-undecane)diethyl]1,2,3,4-butanetetracarboxylate,mixed [1,2,2,6,6-pentamethylpiperidin-4-yl/β,β,β',β'-tetramethyl-3,9-(2,4,8,10-tetraoxaspiro[5.5]-undecane)diethyl]1,2,3,4-butanetetracarboxylate,octamethylene bis(2,2,6,6-tetramethyl-piperidin-4-carboxylate),4,4'-ethylenebis(2,2,6,6-tetramethylpiperazin-3-one),N-2,2,6,6-tetramethyl-piperidin-4-yl-n -dodecylsuccinimide,N-1,2,2,6,6-pentamethyl-piperidin-4-yl-n-dodecylsuccinimide,N-1-acetyl-2,2,6,6-tetramethylpiperidin-4-yl-n-dodecylsuccinimide,1-acetyl13-dodecyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro[4.5]decane-2,4-dione,di-(1-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl) sebacate,di-(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl)succinate,1-octyloxy-2,2,6,6-tetramethyl-4-hydroxy-piperidine,poly-{[6-tert-octylamino-s-triazin-2,4-diyl][2-(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl)imino-hexamethylene-[4-(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl)imino],and2,4,6-tris[N-(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl)-n-butylamino]-s-triazine.

A most preferred hindered amine compound isbis(2,2,6,6-tetramethylpiperidin-4-yl) sebacate,bis(1,2,2,6,6-pentamethylpiperidin-4-yl) sebacate,di(1,2,2,6,6-pentamethylpiperidin-4-yl)(3,5-di-ten-butyl-4-hydroxybenzyl)butylmalonate, the polycondensationproduct of 1-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-hydroxypiperidineand succinic acid, the polycondensation product of2,4-dichloro-6-tert-octylamino-s-triazine and4,4'-hexamethylenebis(amino-2,2,6,6-tetramethylpiperidine),N,N',N",N"'-tetrakis[(4,6-bis(butyl-(2,2,6,6-tetramethyl-piperidin-4-yl)amino)-s-triazine-2-yl]-1,10-diamino-4,7-diazadecane.di-(1-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl) sebacate,di-(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl) succinate,1-octyloxy-2,2,6,6-tetramethyl-4-hydroxy -piperidine,poly-{[6-ten-octylamino-s-triazin-2,4-diyl][2-(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl)imino-hexamethylene-[4-(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl)imino],or2,4,6-tris[N-(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl)-n-butylamino]-s-triazine.

The following examples are presented for the purpose of illustrationonly and are not to be construed to limit the nature or scope of theinstant invention in any manner whatsoever.

EXAMPLE 12-(2-Hydroxy-3-diethylaminomethyl-5-methylphenyl)-2H-benzotriazole

2-(2-Hydroxy-5-methylphenyl)-2H-benzotriazole (74.3 g, 0.33 tool),diethylamine (37.0 g, 0.51 mol) and paraformaldehyde (17.1 g) aredissolved in 85 mL of n-butanol. The mixture is heated with agitation atreflux (95° to 100° C.) for 44 hours. The solvent is then removed byvacuum distillation to give a yellow viscous liquid as product in highyield (>99%). This Mannich base is identified as the above-namedcompound by thin layer chromatography using toluene as the mobile phase.

EXAMPLE 22-(2-Hydroxy-3-diethylaminomethyl-5-tert-octylphenyl)-2H-benzotriazole

2-(2-Hydroxy-5-tert-octylphenyl)-2H-benzotriazole (70.0 g, 0.22 mol),diethylamine (24.3 g, 0.33 tool) and paraformaldehyde (11.2 g) aredissolved in 55 mL of n-butanol. The mixture is heated with agitation atreflux (95° to 100° C.) for 50 hours. The solvent is then removed byvacuum distillation to give an off-white solid as product in high yield(>99%). This Mannich base is identified as the above-named compound bythin layer chromatography using toluene as the mobile phase.

EXAMPLE 32-(Benzotriazol-2-yl)-4-methyl-6-(2-hydroxy-3-benzoyl-6-n-octyloxybenzyl)phenol

2-(2-Hydroxy-3-diethylaminomethyl-5-methylphenyl)-2H-benzotriazole (21.0g, 0.067 mol), 2-hydroxy-4-n-octyloxybenzophenone (22.0 g, 0.067 mol),and p-cymene (80 g) are charged to a reaction flask. The mixture isheated to dissolve, and sodium methoxide (1.0 g, 25% in methanol) isadded as catalyst. The solution is heated with agitation under anitrogen flow at reflux (176°-178° C.) for 24 hours. After cooling toroom temperature, the solution is filtered, and the black filtered solid(˜1 g) is discarded. The product is then precipitated with methanol. Theyellow solid (12.5 g) obtained is vacuum filtered, and identified usingthin layer chromatography, with toluene:acetone (1:1) as the mobilephase. To remove the yellow color, the solid product is dissolved in hottoluene, and silica gel is introduced. The silica gel is gravityfiltered hot. The toluene is removed by vacuum distillation, yielding8.2 g of the title compound as an off-white solid, m.p. 124°-126° C. HNMR shows proton resonances at 0.73 ppm, triplet, 3 protons, (terminal--CH₃ in --OC₈ H₁₇); 1.06-1.24 ppm, complex, 8 protons, (inner 4X-CH₂ in--OC₈ H₁₇); 1.32 ppm, quintet, 2 protons, (--CH₂ beta to Ar--O); 1.71ppm, quintet, 2 protons, (--CH₂ gamma to Ar--O); 2.32 ppm, singlet, 3protons (--CCH₃); 4.03 ppm, triplet, 2 protons, (--CH₂ alpha to Ar-0);4.24 ppm, singlet, 2 protons, (Ar--CH₂ --Ar); 6.48 ppm, doublet, 1proton, (C₈ H₁₇ OCCH--); 6.82 ppm, 1 proton, (CH₃ CCHC--CH₂ --Ar);7.40-7.64 ppm, complex, 6 protons, (Ar--COCCHCH₃ --, C₈ H₁₇OCCHCH--,--NCCHC₂ H₂ --); 7.68 ppm, doublet, 2 protons, (AR--COCCHC₃ H₃CH), 7.95 ppm, complex, 2 protons, (--NCCHC₂ H₂ CH); 8.05 ppm, 1 proton,(CH₃ CCHCNCOH); 11.46 and 12.80 ppm, two singlets, two protons,(exchangeable --OH protons).

Analysis for C₃₅ H₃₇ N₃ O₄ : Calc: C, 74.5; H, 6.6; N, 7.5. Found: C,74.0; H, 6.6; N, 7.4.

EXAMPLE 42-(Benzotriazol-2-yl)-4-methyl-6-(2-hydroxy-3-benzoyl-6-methoxybenzyl)phenol

2-(2-Hydroxy-3-diethylaminomethyl-5-methylphenyl)-2H-benzotriazole (20.0g, 0.064 tool), 2-hydroxy-4-methoxybenzophenone (14.7 g, 0,064 mol), andsodium methoxide (1.0 g, 25% in methanol) are charged to a reactionflask. The mixture is heated to 130° C. and held at this temperature for20 hours with agitation under a nitrogen flow. At that time, the productis identified using thin layer chromatography, with toluene as themobile phase. To the brown-yellow solid is added hot methanol. Theyellow solids are vacuum filtered and triturated twice using methanol,yielding 20.6 g product. To remove the yellow color, the solids aredissolved in hot toluene, and silica gel is introduced. The silica gelis gravity filtered hot. The toluene is removed by vacuum distillation,yielding 12.1 g of the title compound as a pale yellow solid, m.p.206°-209° C.

H NMR shows proton resonances at 2.32 ppm, singlet, 3 protons, (--CCH₃);3.89 ppm, singlet, 3 protons, (--OCH₃); 4.27 ppm, singlet, 2 protons,(Ar--CH₂ --Ar); 6.54 ppm, doublet, 1 proton, (CH₃ OCCH--); 6.76 ppm,singlet, 1 proton (CH₃ CCH--CH₂ --Ar); 7.48-7.60 ppm, complex, 6 protons(Ar--COCCHCHCHCH--); 7.69 ppm, doublet, 2 protons, (Ar--COCCHC₃ H₃ CH);7.95 ppm, complex; 2 protons, (--NCCHC₂ H₂ CH); 8.06 ppm, singlet, 1proton, (CH₃ CHCNCOH); 11.34 and 12.68 ppm, two singlets, two protons,(exchangeable --OH protons).

Analysis for C₂₈ H₂₃ N₃ O₄ : Calcd: C, 72.2; H, 5.0; N, 9.0. Found: C,72.2; H, 4.8; N, 9.8.

EXAMPLE 52-(Benzotriazol-2-yl)-4-tert-octyl-6-(2-hydroxy-3-benzoyl-6-n-octyloxybenzyl)phenol

Methanol (50 ml) is placed into a 300 ml three-necked flask equippedwith a stirrer, thermometer, condenser, Dean-Stark trap and nitrogeninlet. Sodium (0.3 g, 0.013 tool) is added to the methanol and themixture stirred at room temperature till all the sodium is dissolved.Then,2-(2-hydroxy-3-diethylaminomethyl-5-tert-octylphenyl)-2H-benzotriazole(10.2 g, 0.025 mol), 2-hydroxy-4-n-octyloxybenzophenone (8.2 g, 0.025mol) and another 50 ml of methanol are added to the sodium methoxidesolution. The reactants are heated at reflux till half the methanol iscollected in the Dean-Stark trap. o-Xylene (50 ml) is added and thetemperature is raised to the reflux temperature of o-xylene (143°-145°C.) and heating is continued for 24 hours. The mixture is then cooledand acetic acid is added to neutralize the sodium methoxide catalyst.The o-xylene solvent is then removed by vacuum distillation. The crudeproduct obtained is recrystallized from heptane to afford the titlecompound in a yield of 10 g (62 % yield) as a white crystalline solidmelting at 96°-100° C.

Analysis for C₄₂ H₅₁ N₃ O₄ : Calcd: C, 76.2; H, 7.8; N, 6.4. Found: C,76.6; H, 7.9; N, 6.5.

EXAMPLE 6 2-(Benzotriazol- 2- yl )-4-methyl-6-(2-hydroxy-3-benzoyl-6-n-octyloxybenzyl)phenol

Following the general procedure of Example 5 using the Mannichintermediate of Example 1 and 2-hydroxy-4-n-octyloxybenzophenone, thetitle compound is obtained as an off-white crystalline solid melting at128°-130° C.

Analysis for C₃₅ H₃₇ N₃ O₄ : Calcd: C; 74.6; H, 6.6; N, 7.5. Found: C,74.7; H, 6.6; N, 7.5.

EXAMPLE 72-(Benzotriazol-2-yl)-4-tert-octyl-6-(2-hydroxyl-3-benzoyl-6-methoxybenzyl)phenol

Following the general procedure of Example 5 using the Mannichintermediate of Example 2 and 2-hydroxy-4-methoxybenzophenone, the titlecompound is obtained as a yellow crystalline solid melting at 137°-139°C.

Analysis for C₃₅ H₃₇ N₃ O₄ : Calcd: C, 74.6; H, 6.6; N, 7.4. Found: C,74.6; H, 6.7; N, 7.3.

EXAMPLE 82-(Benzotriazol-2-yl)-4-tert-octyl-6-(2-hydroxyl-3-benzoyl-6-dodecyloxybenzyl)phenol

Following the general procedure of Example 5 using the Mannichintermediate of Example 2 and 2-hydroxy-4-dodecyloxybenzophenone, thetitle compound is obtained as a yellow crystalline solid melting at78°-82° C.

Analysis for C₄₅ H₅₉ N₃ O₄ : Calcd: C, 76.9; H, 8.3; N, 5.9. Found: C,77.9; H, 8.5; N, 5.9.

EXAMPLE 92-(Benzotriazol-2-yl)-4-methyl-6-(2-hydroxy-3-benzoyl-6-dodecyloxybenzyl)phenol

Following the general procedure of Example 5 using the Mannichintermediate of Example 1 and 2-hydroxy-4-dodecyloxybenzophenone, thetitle compound is obtained as a yellow crystalline solid melting at100°-105° C.

Analysis for C₃₉ H₄₅ N₃ O₄ : Calcd: C, 75.6; H, 7.3; N, 6.8. Found: C,75.9; H, 7.6; N, 7.2.

EXAMPLES 10-17

Following the general procedure of Example 5 using the Mannichintermediate of Example 1 or 2 and various substituted benzophenones,the following compounds of formula I are prepared as seen in the Tablebelow. The compounds of Examples 3-9 are also included to make the tablecomplete.

    __________________________________________________________________________     ##STR2##                             (I)                                     Example                                                                             T.sub.1                                                                           T.sub.2                                                                            E.sub.1                                                                              E.sub.3                                                                            E.sub.4                                                                              E.sub.6                                     __________________________________________________________________________     3    H   methyl                                                                             n-octyloxy                                                                           H    H      H                                            4    H   methyl                                                                             methoxy                                                                              H    H      H                                            5    H   t-octyl                                                                            n-octyloxy                                                                           H    H      H                                            6    H   methyl                                                                             n-octyloxy                                                                           H    H      H                                            7    H   t-octyl                                                                            methoxy                                                                              H    H      H                                            8    H   t-octyl                                                                            dodecyloxy                                                                           H    H      H                                            9    H   methyl                                                                             dodecyloxy                                                                           H    H      H                                           10    Cl  methyl                                                                             n-octyloxy                                                                           H    H      H                                           11    H   t-octyl                                                                            i-octyloxy                                                                           H    H      H                                           12    H   methyl                                                                             methoxy                                                                              SO.sub.3 H                                                                         H      H                                           13    Cl  t-octyl                                                                            hydroxy                                                                              H    H      H                                           14    H   methyl                                                                             methoxy                                                                              H    methoxy                                                                              hydroxy                                     15    H   t-octyl                                                                            hydroxy                                                                              H    hydroxy                                                                              hydroxy                                     16    H   methyl                                                                             methoxy                                                                              SO.sub.3 H                                                                         methoxy                                                                              hydroxy                                     17    H   t-octyl                                                                            methoxy                                                                              H    H      hydroxy                                     __________________________________________________________________________

EXAMPLE 18 Thermogravimetric Data

Using a standard thermogravimetric instrument (TA Instruments Model2950, Thermogravimetric Analyzer), the following isothermal and scanningthermogravimetric data are determined on selected 2H-benzotriazoles, onselected benzophenones and the instant hybrid compounds of thisinvention. These data are given in the Table below.

    ______________________________________                                                 Isothermal at 250° C.                                                                 Scanning at 10° C./min                                  100 ml/min N.sub.2 purge                                                                     100 ml/min N.sub.2 purge                                       Time in minutes to                                                                           Temperature °C. at                                      Indicated Weight                                                                             Indicated Weight                                      Compound of                                                                            Loss of Stabilizer                                                                           Loss of Stabilizer                                    Example* 10%       50%      10%      50%                                      ______________________________________                                        A        3.5       8.1      218      260                                      B        5.9       10.1     253      295                                      C        --        <5       206      247                                      D        <1        11       249      291                                      E        (<1) 30   --       343      386                                      3        (<1) 30   --       380      419                                      4        (<5) 30   --       357      405                                      ______________________________________                                         *A is 2(2-hydroxy-5-methylphenyl)-2H-benzotriazole.                           B is 2(2-hydroxy-5-tert-octylphenyl)-2H-benzotriazole.                        C is 2hydroxy-4-methoxybenzophenone.                                          D is 2hydroxy-4-n-octyloxybenzophenone.                                       E is 2,2'-methylenebis[4-methyl-6-(benzotriazol-2-yl)phenol].            

This instant compounds are certainly more resistant to volatilizationand loss under high temperature conditions than are the simple2H-benzotriazoles and benzophenones. Even the dimeric 2H-benzotriazoledescribed in U.S. Pat. No. 5,166,355 is less resistant to heat loss thanare the instant compounds.

EXAMPLE 19 Spectral Properties

The following table shows the absorption maxima and molar extinctioncoefficients of a number of instant compounds. State-of-the-artcommercial benzotriazole and benzophenone UV-absorbers and a number ofinstant compounds are tested. The concentrations of each of the samplesare identical, namely 20 mg/L. The high molar extinction coefficientsfor the instant compounds allow said compounds to be at lowerconcentrations while still affording excellent UV light stabilizationprotection.

    ______________________________________                                        Absorption Maxima and Molar Extinction Coefficients                           Compound of nm     Molar ε                                                                          nm   Molar ε                            ______________________________________                                        A*          295     9,700     340  15,900                                     C*          300    30,200     342  23,700                                     D*          294    15,700     324  11,250                                     Example 3   300    30,200     342  23,700                                     Example 4   302    39,100     340  28,000                                     ______________________________________                                         *A is 2(2-hydroxy-5-methylphenyl)-2H-benzotriazole.                           C is 2hydroxy-4-methoxybenzophenone.                                          D is 2hydroxy-4-n-octyloxybenzophenone.                                  

The absorption properties of the instant compounds show that saidcompounds would provide very effective light stabilization protection tosubstrates from the deleterious effects of actinic light.

What is claimed is:
 1. A compound of formula I ##STR3## wherein T₁ ishydrogen, chloro, alkyl of 1 to 4 carbon atoms or --SO₃ H,T₂ is alkyl of1 to 12 carbon atoms, E₁ is hydrogen, chloro or --OE₂, E₂ is hydrogen oralkyl of 1 to 18 carbon atoms, E₃ is hydrogen, alkyl of 1 to 4 carbonatoms, chloro or --SO₃ H, E₄ is hydrogen, chloro or --OE₅, E₅ ishydrogen or alkyl of 1 to 18 carbon atoms, and E₆ is hydrogen, hydroxylor carboxy.
 2. A compound according to claim 1 wherein T₁ is hydrogen orchloro.
 3. A compound according to claim 2 wherein T_(l) is hydrogen. 4.A compound according to claim 1 wherein T₂ is alkyl of 1 to 12 carbonatoms.
 5. A compound according to claim 4 wherein T₂ is alkyl of 1 to 8carbon atoms.
 6. A compound according to claim 1 wherein E₁ is --OE₂where E₂ is hydrogen or alkyl of 1 to 12 carbon atoms.
 7. A compoundaccording to claim 6 wherein E₁ is --OE₂ where E₂ is hydrogen or alkylof 1 to 8 carbon atoms.
 8. A compound according to claim 1 wherein E₃ ishydrogen.
 9. A compound according to claim 1 wherein E₄ is hydrogen or--OE₅ where E₅ is hydrogen or alkyl of 1 to 12 carbon atoms.
 10. Acompound according to claim 9 wherein E₄ is --OE₅ where E₅ is hydrogenor alkyl of 1 to 4 carbon atoms.
 11. A compound according to claim 1wherein E₆ is hydrogen or hydroxyl.
 12. A compound according to claim 1wherein T₁ is hydrogen or chloro, T₂ is alkyl of 1 to 12 carbon atoms,E₁ is --OE₂ where E₂ is hydrogen of alkyl of 1 to 12 carbon atoms, E₃ ishydrogen, E₄ is hydrogen or --OE₅ where E₅ is hydrogen or alkyl of 1 to12 carbon atoms, and E₆ is hydrogen or hydroxyl.
 13. A compoundaccording to claim 12 wherein T₁ is hydrogen, T₂ is alkyl of 1 to 8carbon atoms, E₁ is --OE₂ where E₂ is alkyl of 1 to 12 carbon atoms, andeach of E₃, E₄ and E ₆ is hydrogen.
 14. The compound according to claim1 which is(a)2-(benzotriazol-2-yl)-4-methyl-6-(2-hydroxy-3-benzoyl-6-n-octyloxybenzyl)phenol;(b)2-(benzotriazol-2-yl)-4-methyl-6-(2-hydroxy-3-benzoyl-6-methoxybenzyl)phenol;(c)2-(benzotriazol-2-yl)-4-tert-octyl-6-(2-hydroxy-3-benzoyl-6-n-octyloxybenzyl)phenol;(d)2-(benzotriazol-2-yl)-4-methyl-6-(2-hydroxy-3-benzoyl-6-dodecyloxybenzyl)phenol;(e)2-(benzotriazol-2-yl)-4-tert-octyl-6-(2-hydroxy-3-benzoyl-6-methoxybenzyl)phenol;or (f)2-(benzotriazol-2-yl)-4-tert-octyl-6-(2-hydroxy-3-benzoyl-6-dodecyloxybenzyl)phenol.